CN101625326B - Molecular photodissociation ionization velocity imaging device - Google Patents
Molecular photodissociation ionization velocity imaging device Download PDFInfo
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- CN101625326B CN101625326B CN2009100550852A CN200910055085A CN101625326B CN 101625326 B CN101625326 B CN 101625326B CN 2009100550852 A CN2009100550852 A CN 2009100550852A CN 200910055085 A CN200910055085 A CN 200910055085A CN 101625326 B CN101625326 B CN 101625326B
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Abstract
The invention discloses a molecular photodissociation ionization velocity imaging device and relates to a device which uses the ion velocity imaging technology for carrying out slicing and imaging on positive and negative ions and electronic three-dimensional information. The device comprises an inert gas carrier gas source, a pressure reducing valve, a sample cell, a vacuum cavity, a pre-stage dry pump, a molecular pump, a pulse valve, a skimmer, an ion lens group, a micro-channel plate, a fluorescent plate, a CCD camera, a computer and a synchronized laser source. The device designs an ion lens in the traditional ion velocity imaging system to the multi-stage ion lenses and combines the micro-channel plate with rapid response, the fluorescent plate and the enhanced CCD camera with ultra-high time resolution, thereby greatly extending an ion cloud on time scale, leading the ion slicing and imaging precision to achieve 5ns, improving the time resolution, solving the problem of image blur and reducing the cost.
Description
Technical field
The invention belongs to the molecular reaction dynamics field, relate to the ion velocity imaging technique three-dimensional information of negative ions and electronics is carried out slice imaging, specifically a kind of molecular photodissociation ionization velocity imaging device.
Background technology
Molecular photodissociation dynamics is a key areas of molecular reaction dynamics.Photodissociation dynamics is not only studied the interaction of monomer molecule and laser, and is the control bimolecular, even the important means of polymolecular system chemical reaction.Because in recent years, preparation for selected interior energy state, obtain specific reaction product or select specific reaction channel to become the focus and the focus of molecular reaction dynamics, therefore, it is essential that the quantum state, particularly its angular distribution and velocity distribution of measurement relative photo hydrolysis products or photolysis debris just becomes.
From eighties of last century seventies, people measure the quantum state layout of different products with regard to the method that begins to utilize spectrum, perhaps utilize translation energy-mass spectrometry method to measure the velocity distribution of product.The two is combined just develop the interior energy state that to measure product simultaneously and the technology of relevant speed, strengthen multiphoton ionization-flying time technology and Doppler's spectral technique as resonance.The projection in one direction but defective of these two kinds of technology is all can only measuring speed to distribute, the angular distribution of inverting reaction kinetics initial time that can not be complete.
The later stage eighties, particularly the mid-90 the velocity imaging technology maturation, make the ion velocity imaging method become the technology of optimal photodissociation dynamic experiment.The ion velocity imaging technique is on the basis that is similar to the time of-flight mass spectrometer device, introduces ion lens, to the locus difference, but the ion that speed is identical converges, make their distribute same positions of responsive detectors on the throne, and connect fluorescent plate, use the CCD camera imaging at last thereafter.Its advantage is that behind linearly polarized light that is parallel to detector surface and example reaction, the ion that is produced is because of the different images that form Two dimensional Distribution in detector surface of its speed.This image is carried out contrary Abel transformation or Hankel transform, can obtain the whole three dimensional velocity distribution of different products on homomorphism not.But shortcoming is, has limited the polarization direction of laser, and has suffered in the process of Flame Image Process and to have introduced a large amount of man made noises.
Entered since 21 century, along with the further investigation of people to molecular reaction dynamics, it is found that " cross section, equator " in reaction product or the fragment ion distributed in three dimensions in fact comprised all angles and velocity information, if therefore can directly obtain the sectioning image in " cross section, equator ", so just do not need image is carried out the conversion of 2 d-to-3 d, the man made noise will can not be introduced into simultaneously, the polarization direction of laser also no longer is restricted, so the slice imaging technology becomes the important means of understanding the reaction kinetics process.2003, the method that Kitsopoulos group utilizes pulsed field to control successfully realized the section to ion cloud.They have added two high-voltage pulse fields in the system of original ion velocity imaging, one of them is used for controlling the delay of ion lens high pressure, thereby obtain longer ion cloud; Another one is used for controlling MCP and carries out gate, chooses suitable sectioning image.The shortcoming of this method is, the high-voltage pulse of fast rising edge is difficult to obtain, and therefore the precision of section can not be very high, and can make image blur.
Summary of the invention
The purpose of this invention is to provide a kind of molecular photodissociation ionization velocity imaging device, this device is on traditional ion velocity imaging technique basis, adopted the mode of multistage ion lens, and the length in the ion flight chamber of having extended, make the time scale of ion cloud diffusion reach a hundreds of nanosecond, utilize response microchannel plate fast simultaneously, signal is the fluorescent plate of decay fast, and the enhancement mode CCD camera of superelevation temporal resolution carries out imaging, the time precision that has guaranteed section reaches nanosecond order, make the precision of slice imaging and accuracy all improve greatly, and avoided the image blurringization problem that causes by the high-voltage pulse field.
The concrete technical scheme that realizes the object of the invention is:
A kind of molecular photodissociation ionization velocity imaging device, this device comprises: inert gas carrier gas source, reduction valve, the first carrier gas pipe, sample cell, the second carrier gas pipe, vacuum cavity, the dried pump of prime, molecular pump, pulse valve, strainer, ion lens, microchannel plate, fluorescent plate, the pulse power, first high-voltage DC power supply, second high-voltage DC power supply, the 3rd high-voltage DC power supply, CCD camera, computing machine, laser and two-dimensional adjustment dish;
Vacuum cavity is formed by connecting by a horizontally set and two square circular cylindrical cavities that vertically are provided with, and its strainer is located at perforation place in two cavitys, and two cavitys are respectively equipped with dried pump of prime and molecular pump; Vertically be provided with pulse valve in the cavity that is provided with, be provided with ion lens, microchannel plate and fluorescent plate in the cavity of horizontally set;
The reduction valve two ends connect the inert gas carrier gas source and the first carrier gas pipe respectively, and the first carrier gas pipe stretches into sample cell, port is positioned at below the sample liquid liquid level, and sample cell is airtight; The second carrier gas Guan Yiduan stretches into sample cell, is positioned at more than the sample liquid liquid level, and the other end passes the vacuum cavity body wall and is connected with its interior pulse valve; Pulse valve is connected to the outer pulse power of vacuum cavity; Strainer places on the center line of pulse valve, and is coaxial with pulse valve;
The two-dimensional adjustment dish places the cavity top of vertical setting, and in the form of annular discs, centre bit is equipped with aperture, and is coaxial with pulse valve; The second carrier gas pipe links to each other with pulse valve by this aperture; The two-dimensional adjustment dish comprises two groups of orthogonal fine adjustment screw rods, and two groups of bars move 0～28mm respectively on both direction, with the position of this regulating impulse valve, guarantees that pulse molecular beam and the position of synchronous laser at ion lens interact;
Ion lens comprises: first pole plate, second pole plate, tri-electrode, quadripolar plate and drift utmost point pole plate group, each plate are the center and have the stainless steel plectane of circular hole and place along horizontally set cavity axis; Drift level step group is made up of nine blocks of identical stainless steel plectanes that connect successively; First pole plate, second pole plate, tri-electrode and quadripolar plate are connected respectively to the first outer high-voltage DC power supply of vacuum cavity, drift utmost point pole plate winding ground; The center line of pulse valve and strainer and horizontally set cavity axis normal and be positioned at first pole plate, the center between second pole plate;
Microchannel plate and fluorescent plate place on the inwall at vacuum cavity flange-interface place and are coaxial with ion lens; The two ends of microchannel plate are connected respectively to the second outer high-voltage DC power supply of vacuum cavity, and fluorescent plate is connected to the 3rd outer high-voltage DC power supply of vacuum cavity; It is outer, coaxial with microchannel plate and fluorescent plate that the CCD camera is arranged at vacuum cavity; The CCD camera connects computing machine;
Laser incides the center of first pole plate and second pole plate, perpendicular to the central axis of horizontal cavity, perpendicular to the center line of pulse valve and strainer;
The dried pump of prime is communicated with molecular pump; Dried pump of prime and molecular pump guarantee that the operating pressure of vacuum cavity is 10
-6～10
-7Mbar.
Described first pole plate, second pole plate, tri-electrode, quadripolar plate is respectively diameter 135～145mm, thickness 1～2mm, the stainless steel plectane of aperture 5mm～40mm; Each pole plate diameter 135～145mm in the drift utmost point pole plate group, thickness 8～12mm, aperture 80～120mm, all pole plates keep specific distance between any two; All pole plates load different voltage, and the voltage ratio between pole plate and the pole plate is set at different value at different ions.
The horizontal flight cavity length of described vacuum cavity is 1000～1500mm, and is coaxial with ion lens, microchannel plate and fluorescent plate.
Described microchannel plate adopts response high sensitivity microchannel plate fast, and signal response time is less than 500ps; The fluorescence decay time of fluorescent plate (signal intensity decays to 10% from 90%) is less than 100ns.
Described CCD camera adopts the time-resolved enhancement mode CCD camera of nanosecond, and minimum exposure time is not more than 2ns.
The described pulse power provides the pulse power for pulse valve; First high-voltage DC power supply is respectively first pole plate, second pole plate, and tri-electrode, quadripolar plate, drift utmost point pole plate group is just providing/negative high voltage; Second high-voltage DC power supply provides high pressure for microchannel plate; The 3rd high-voltage DC power supply provides high pressure for fluorescent plate.
Advantage of the present invention is: improved the temporal resolution of ion velocity imaging technique greatly, made the precision of slice imaging and accuracy all improve greatly, and avoided the image blurringization problem that caused by the high-voltage pulse field.
Description of drawings
Fig. 1 is a structural representation of the present invention
Fig. 2 is an intermediate ion lens synoptic diagram of the present invention
Fig. 3 is during for the long 1000mm of flight cavity, the focusing effect figure of ion lens
Fig. 4 is during for the long 500mm of flight cavity, the focusing effect figure of ion lens
Fig. 5 is during for the long 1000mm of flight cavity, the drawing effect figure of ion cloud
Fig. 6 is during for the long 500mm of flight cavity, the drawing effect figure of ion cloud
Embodiment
The invention will be further described below in conjunction with accompanying drawing:
Consult Fig. 1, among the figure: 1 is the inert gas carrier gas source, and 2 is reduction valve, 3 is the first carrier gas pipe, and 4 is sample cell, and 5 is the second carrier gas pipe, 6 is vacuum cavity, and 7 is the dried pump of prime, and 8 is molecular pump, 9 is pulse valve, and 10 is strainer, and 11 is first pole plate, 12 is second pole plate, and 13 is tri-electrode, and 14 is quadripolar plate, 15 are drift utmost point pole plate group, and 16 is microchannel plate, and 17 is fluorescent plate, 18 is the pulse power, 19 is first high-voltage DC power supply, and 20 is second high-voltage DC power supply, and 21 is the 3rd high-voltage DC power supply, 22 is the CCD camera, 23 is computing machine, and 24 is laser, and 25 is the two-dimensional adjustment dish.
Consult Fig. 2, among the figure: 11 is first pole plate, and 12 is second pole plate, 13 is tri-electrode, 14 is quadripolar plate, and 15 are drift utmost point pole plate group, and 16 is microchannel plate, 17 is fluorescent plate, 19 is first high-voltage DC power supply, and 20 is second high-voltage DC power supply, and 21 is the 3rd high voltage direct current, 24 is synchronous laser, and " " locates to be synchronous laser 24 and molecular beam interaction point.
Fig. 3, Fig. 4 be ion lens in the different flight cavity of length, for the focusing performance figure of same ion, long during for 1000mm when flight cavity, the focusing multiple of ion is 80; When flight cavity length was 500mm, the focusing multiple of ion was 16.7.
Fig. 5, Fig. 6 be ion lens in the different flight cavity of length, for the drawing effect figure of same ion group, long during for 1000mm when flight cavity, ionic group can be stretched to 263ns; When flight cavity length was 500mm, ionic group can be stretched to 142ns.
Consult Fig. 1, the present invention is made up of inert gas carrier gas source 1, reduction valve 2, the first carrier gas pipe 3, sample cell 4, the second carrier gas pipe 5, vacuum cavity 6, the dried pump 7 of prime, molecular pump 8, pulse valve 9, strainer 10, ion lens, microchannel plate 16, fluorescent plate 17, the pulse power 18, first high-voltage DC power supply 19, second high-voltage DC power supply 20, the 3rd high-voltage DC power supply 21, CCD camera 22, computing machine 23, laser 24 and two-dimensional adjustment dish 25.
Vacuum cavity 6 is formed by connecting by a horizontally set and two circular cylindrical cavities that vertically are provided with, and its strainer 10 is located at perforation place in two cavitys, and two cavitys are respectively equipped with dried pump 7 of prime and molecular pump 8; Vertically be provided with pulse valve 9 in the cavity that is provided with, be provided with ion lens, microchannel plate 16 and fluorescent plate 17 in the cavity of horizontally set.
Reduction valve 2 two ends connect inert gas carrier gas source 1 respectively and the first carrier gas pipe, 3, the first carrier gas pipes 3 are connected with sample cell 4, sample cell 4 sealings, and after putting into sample in the sample cell 4, the first carrier gas pipe, 3 ends are positioned at below the sample liquid liquid level; 5 one sections of the second carrier gas pipes are connected with sample cell 4, and the other end passes the vacuum cavity body wall and is connected with pulse valve 9, sample cell 4 sealings, and after putting into sample in the sample cell 4, the second carrier gas pipe, 5 one ends are positioned at more than the sample liquid liquid level; Pulse valve 9 is connected to the pulse power 18 outside the vacuum cavity 6; Strainer 10 places on the center line of pulse valve 9, and is coaxial with pulse valve 9.
Two-dimensional adjustment dish 25 places vacuum cavity 6 tops, and in the form of annular discs, centre bit is equipped with aperture, and is coaxial with pulse valve 9, and the second carrier gas pipe 5 links to each other with pulse valve 9 by this aperture.Two-dimensional adjustment dish 25 comprises two groups of orthogonal fine adjustment screw rods, two groups of bars can move 0～28mm respectively on both direction, position with this regulating impulse valve 9, can guarantee that not only pulse molecular beam and synchronous laser 24 are at first pole plate 11, center between second pole plate 12 interacts, and can so that fragment ion in the imaging of the optimum position of ion lens.
Ion lens comprises: first pole plate 11, second pole plate 12, tri-electrode 13, quadripolar plate 14 and drift utmost point pole plate group 15, and a drift grade step group 15 is made up of 9 blocks of identical stainless steel plectanes that connect successively; Each plate is the center and has the stainless steel plectane of circular hole and place along the horizontal flight chamber center line of vacuum cavity 6, and the design in this horizontal flight chamber is different from traditional time-flight cavity and common ion velocity imaging chamber, and its length is longer, about 1000mm.First pole plate 11, second pole plate 12, tri-electrode 13 and quadripolar plate 14 are connected respectively to the first outer high-voltage DC power supply 19 of vacuum cavity, drift utmost point pole plate group 15 ground connection; The center line of pulse valve 9 and strainer 10 is vertical with the transverse chambers body axis of vacuum cavity 6, and the center between first pole plate 11 and second pole plate 12; First pole plate 11, second pole plate 12, tri-electrode 13, quadripolar plate 14 and drift utmost point pole plate group 15 and microchannel plate 16, fluorescent plate 17 are coaxial.Multistage ion lens has two advantages in conjunction with the design of lengthening flight cavity for the section velocity imaging: the first, and the focusing effect of ion is better; The second, the drawing effect of ionic group is more obvious.
The dried pump 7 of prime is communicated with molecular pump 8, and molecular pump 8 is communicated with vacuum cavity 6; Dried pump 7 of prime and molecular pump 8 guarantee that the pressure of vacuum cavity 6 is 10
-6～10
-7Mbar.
Workflow of the present invention is:
Operating pressure in the whole vacuum chamber 6 of the guarantee of work of dried pump 7 of prime and molecular pump 8 is 10
-6～10
-7Between the mbar, 2 decompressions enter sample cell 4 by the first carrier gas pipe 3 later to gas in the rare gas carrier gas source 1 through reduction valve, sample cell is the testing liquid sample, when being positioned at the following carrier gas pipe of liquid level and emitting gas, the testing sample of part vaporization is carried out and process carrier gas pipe 5 arrival pulse valves 9, after the calibration through two-dimensional adjustment dish 25, the molecular beam of pulse valve 9 ejection will fly to the centre position of first pole plate 11 and second pole plate 12 behind strainer 10 collimations, and will interact at same position with synchronous laser 24.Through after the effect of femtosecond laser, COULOMB EXPLOSION will take place the molecule in the molecular beam or the ionization of dissociating is ion.Ion or electronics for opposed polarity, first pole plate, 11, the second pole plates, 12, the tri-electrodes 13, quadripolar plate 14 will load different positive high voltages or negative high voltage respectively, guarantee different spatial in the ionic group but the identical ion incidence of speed to the same position of microchannel plate 16.Because the length of flight cavity is about 1000mm～1200mm, ionic group will be stretched to the hundreds of scope of a nanosecond, at this moment, regulate sweep interval and scanning gate-width in the CCD camera 20, will gather one by one behind the image integration on the fluorescent plate 17.So just obtained the sectioning image information of different ions signal, by analysis to these images, overall process that just can the inverting molecular reaction dynamics.
Claims (2)
1. a molecular photodissociation ionization velocity imaging device is characterized in that this device comprises: inert gas carrier gas source (1), reduction valve (2), the first carrier gas pipe (3), sample cell (4), the second carrier gas pipe (5), vacuum cavity (6), the dried pump of prime (7), molecular pump (8), pulse valve (9), strainer (10), ion lens, microchannel plate (16), fluorescent plate (17), the pulse power (18), first high-voltage DC power supply (19), second high-voltage DC power supply (20), the 3rd high-voltage DC power supply (21), CCD camera (22), computing machine (23), laser (24) and two-dimensional adjustment dish (25);
Vacuum cavity (6) is formed by connecting by a horizontally set and two circular cylindrical cavities that vertically are provided with, and strainer (10) is located at perforation place in two cavitys, and two cavitys are respectively equipped with dried pump of prime (7) and molecular pump (8); Vertically be provided with pulse valve (9) in the cavity that is provided with, be provided with ion lens, microchannel plate (16) and fluorescent plate (17) in the cavity of horizontally set;
Reduction valve (2) two ends connect the inert gas carrier gas source (1) and the first carrier gas pipe (3) respectively, and the first carrier gas pipe (3) stretches into sample cell (4), and port is positioned at below the sample liquid liquid level, and sample cell (4) is airtight; The second carrier gas pipe (5) one ends are connected with sample cell (4), and its port is arranged in more than sample cell (4) the sample liquid liquid level, and the other end passes vacuum cavity (6) body wall and is connected with its interior pulse valve (9); Pulse valve (9) is connected to the outer pulse power (18) of vacuum cavity (6); Strainer (10) places on the center line of pulse valve (9), and is coaxial with pulse valve (9);
Ion lens comprises: first pole plate (11), second pole plate (12), tri-electrode (13), quadripolar plate (14) and a drift level pole plate group (15), each plate are the center and have the stainless steel plectane of circular hole and place along horizontally set cavity axis; Drift level pole plate group (15) is made up of nine blocks of identical stainless steel plectanes that connect successively; First pole plate (11), second pole plate (12), tri-electrode (13) and quadripolar plate (14) are connected respectively to outer first high-voltage DC power supply (19) of vacuum cavity (6), drift level pole plate group (15) ground connection; The center line of pulse valve (9) and strainer (10) and horizontally set cavity axis normal and be positioned at first pole plate (11), the center between second pole plate (12);
Two-dimensional adjustment dish (25) places the cavity top of vertical setting, and in the form of annular discs, centre bit is equipped with aperture, and is coaxial with pulse valve (9); The second carrier gas pipe (5) links to each other with pulse valve (9) by this aperture; Two-dimensional adjustment dish (25) comprises two groups of orthogonal fine adjustment screw rods, two groups of bars move 0～28mm respectively on both direction, position with this regulating impulse valve (9), guarantee pulse molecular beam and synchronous laser (24) in first pole plate (11), the center between second pole plate (12) interacts;
Microchannel plate (16) and fluorescent plate (17) place on the inwall at vacuum cavity (6) flange-interface place and are coaxial with ion lens; The two ends of microchannel plate (16) are connected respectively to outer second high-voltage DC power supply (20) of vacuum cavity (6); Fluorescent plate (17) is connected to outer the 3rd high-voltage DC power supply (21) of vacuum cavity (6); CCD camera (22) is arranged at outside the vacuum cavity (6), and is coaxial with microchannel plate (16) and fluorescent plate (17); CCD camera (22) connects computing machine (23); The horizontal flight cavity length of vacuum cavity (6) is 1000～1500mm, and is coaxial with ion lens, microchannel plate (16) and fluorescent plate (17); Microchannel plate (16) adopts response high sensitivity microchannel plate fast, and signal response time is less than 500ps; The fluorescence decay time of fluorescent plate (17) is less than 100ns; CCD camera (22) adopts the time-resolved enhancement mode CCD camera of nanosecond, and minimum exposure time is not more than 2ns;
Laser (24) incides the center between first pole plate (11) and second pole plate (12), perpendicular to the axis of horizontal cavity, perpendicular to the center line of pulse valve (9) and strainer (10);
The dried pump of prime (7) is communicated with molecular pump (8); Dried pump of prime (7) and molecular pump (8) guarantee that the operating pressure of vacuum cavity (6) is 10
-6～10
-7Mbar.
2. molecular photodissociation ionization velocity imaging device according to claim 1 is characterized in that first pole plate (11), second pole plate (12), tri-electrode (13), quadripolar plate (14) is respectively diameter 135～145mm, thickness 1～2mm, the stainless steel plectane of aperture 5mm～40mm; Each pole plate diameter 135～145mm in the drift level pole plate group (15), thickness 8～12mm, aperture 80～120mm, each pole plate loads different voltage, and the voltage ratio between pole plate and the pole plate is set at different value at different ions.
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| CN2009100550852A CN101625326B (en) | 2009-07-21 | 2009-07-21 | Molecular photodissociation ionization velocity imaging device |
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| CN101859431B (en) * | 2010-05-12 | 2012-03-14 | 中国科学技术大学 | Method for processing ion velocity slice image |
| CN103762149B (en) * | 2013-12-31 | 2015-11-18 | 华中科技大学 | A kind of device improving velocity of electrons imaging resolution |
| CN104934288B (en) * | 2015-05-12 | 2017-04-12 | 南京信息工程大学 | High time resolution ion speed imager based on tetra-pole plate design |
| CN105789021B (en) * | 2016-02-05 | 2019-03-26 | 南京信息工程大学 | The ion lens device of bipolar light electronic light ion imaging instrument |
| CN107633996B (en) * | 2017-08-28 | 2024-03-08 | 广西电网有限责任公司电力科学研究院 | High-pressure gas miniature mass spectrometry analysis sampling system in sulfur hexafluoride electrical equipment |
| CN109192648B (en) * | 2018-08-09 | 2023-09-15 | 金华职业技术学院 | Free radical photo-product testing method |
| CN110824807A (en) * | 2019-12-13 | 2020-02-21 | 中国科学技术大学 | Method for generating hydrogen free radical beam source with adjustable speed |
| CN113281005B (en) * | 2021-05-13 | 2022-09-06 | 中国科学技术大学 | Device for preparing molecular beam source by laser |
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